JP4194099B2 - LIGHT TRANSMITTER AND LIGHTING DEVICE USING THE LIGHT TRANSMITTER - Google Patents

Description

  The present invention relates to optical signal transmission for in-vehicle wiring, mobile wiring, FA equipment wiring, etc., optical sensors such as liquid level sensors and pressure sensors, image guides for endoscopes, etc., light guide for optical equipment, and mobile phones.・ Digital camera ・ Watch ・ Car audio ・ Car navigation ・ Pachinko stand ・ Slot stand ・ Vending machine ・ Vehicle interior and exterior ・ Dog collar ・ Kitchen ・ Traffic sign ・ Washing stand ・ Shower ・ Bath water temperature display ・ OA equipment ・Light transmission body suitable for illumination and lighting of household electrical appliances, optical equipment, various building materials, staircases, handrails, train platforms, outdoor signboards, etc., and backlights for liquid crystal display units, and lighting using this light transmission body The present invention relates to a device and a method for manufacturing the optical transmission body, and in particular, since it is flexible and excellent in flexibility, it can be easily arranged in an arbitrary shape, and can be disposed at high temperature and high humidity. There is almost no decrease in the amount of emitted light in warm water and in conditions that are exposed to direct sunlight or wind and rain for a long period of time, and excellent emission characteristics can be maintained stably for a long period of time, and it can be placed on a flat surface or the like. The present invention relates to a device that can be fixed more easily and reliably.

  Conventionally, an optical transmission body composed of a core and a clad, which emits light incident from at least one end in the length direction from the other end or the circumferential direction (side surface), and a linear combination of the optical transmission body and a light source Various lighting devices have been proposed.

  Examples of this type of optical transmission member include a transparent core material and a clad material having a refractive index smaller than that of the core material. Here, the core material is a (meth) acrylic polymer such as methyl methacrylate (MMA), and the clad material is vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer (THV), tetrafluoroethylene- Fluoropolymers such as hexafluoropropylene copolymer (FEP) are mentioned as preferable materials (for example, refer to Patent Document 1, Patent Document 2, and Patent Document 3).

  As another optical transmission body, for example, a transparent cylindrical core material and a transparent clad material having a refractive index lower than that of the core material are used, and light is emitted from an optical member provided on the end face. There is a configuration one. Here, the core material is silicone polymer such as silicone rubber and silicone resin, and the cladding material is vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer (THV), tetrafluoroethylene-hexafluoride. Fluoropolymers such as propylene copolymer (FEP) are mentioned as preferable materials (see, for example, Patent Document 4 and Patent Document 5).

  In addition, Patent Documents 6 to 11 have been filed by the applicant as inventions related to the present invention.

Japanese Patent Laid-Open No. 2001-74943 JP 2002-148451 A JP 2000-131529 A Japanese Patent Laid-Open No. 11-142653 JP 2000-32444 A International Publication No. 03/021309 Japanese Patent Application No. 2002-310639 Japanese Patent Application No. 2003-9743 Japanese Patent Application No. 2003-125032 Japanese Patent Application No. 2003-146813 Japanese Patent Application No. 2003-162432

  However, the conventional configuration has the following problems. First, since the optical transmission bodies disclosed in Patent Documents 1 to 3 are inferior in flexibility, the disposition workability is poor, and it is difficult to dispose them in an arbitrary shape as the diameter increases. At the same time, when used with bending, there is a drawback that the usage is limited because of a significant decrease in the amount of light and an increase in the transmission loss value. Furthermore, since this optical transmission body is very hard, there is a large loss when light is introduced simply by cutting the end face, so the amount of emitted light is significantly reduced, and at least the incident end must be polished, resulting in high costs. There was also the fault that it would end up.

  Next, since the optical transmission bodies disclosed in Patent Document 4 and Patent Document 5 are soft and excellent in flexibility, they can be easily arranged in an arbitrary shape even when the diameter is increased, Under normal conditions, there is almost no decrease in the amount of emitted light, and it has excellent emission characteristics. However, there is a drawback that the amount of emitted light is significantly reduced due to white turbidity under high temperature and high humidity conditions or in warm water.

  On the other hand, the present applicant solves the above problem by using an optical transmission body using an amorphous core material having at least a polymer composed of a polymer polyol and a hydroxy group-reactive polyfunctional compound as a core material. We have invented what can be solved, and have previously filed patent applications (see Patent Documents 6 to 9). Subsequent to this application, the applicant is examining an application of the optical transmission body that can be more easily and reliably fixed when placed on a flat surface or the like. Patent applications (see Patent Documents 10 and 11) )is doing. In order to further develop these applications, the applicant has studied the improvement of the weather resistance characteristics of the optical transmission body so far in consideration of the use in applications exposed to direct sunlight and wind and rain for a long time.

  The present invention has been made to solve such problems of the prior art, and the object of the present invention is to be flexible and flexible so that it can be easily formed into an arbitrary shape even when the diameter is increased. In addition to being able to be installed, there is almost no drop in the amount of light emitted under conditions of high temperature and high humidity, warm water, and exposure to direct sunlight or wind and rain for a long period of time. It is an object of the present invention to provide an optical transmission body that can be maintained and a lighting device using the optical transmission body.

In order to achieve the above object, an optical transmission body according to claim 1 of the present invention includes a tubular clad material and an amorphous material that is accommodated in the tubular clad material and has a higher refractive index than the inner surface of the tubular clad material. The amorphous core material includes at least a polymer composed of a polymer polyol and a hydroxy group-reactive polyfunctional compound, and a semicarbazone-based light stabilizer as constituent components. It is characterized by this.
An optical transmission body according to claim 2 is an optical transmission comprising a tubular clad material and an amorphous core material housed in the tubular clad material and having a higher refractive index than the inner surface of the tubular clad material. In the body, the above-mentioned amorphous core material has at least a constituent which is a non-fluidized polymer only by polymerization of a polymer polyol and a hydroxy group-reactive polyfunctional compound, and a semicarbazone light stabilizer. It is characterized by .
The light transmitter according to claim 3 is characterized in that the semicarbazone light stabilizer is a non-aromatic compound.
The optical transmitter according to claim 4 is characterized in that the hydroxy group-reactive polyfunctional compound is composed of a compound having an isocyanate group.
The optical transmitter according to claim 5 is characterized in that the hydroxy group-reactive polyfunctional compound is composed of a functional group derived from an isocyanate group.
An optical transmission body according to claim 6 is characterized in that the one having a functional group derived from the isocyanate group contains an isocyanurate bond.
The optical transmission body according to claim 7 is characterized in that the amorphous core material having at least a polymer composed of the polymer polyol and the hydroxy group-reactive polyfunctional compound as a constituent component is at least partially a gel-like material. It is characterized by including.
The optical transmission body according to claim 8 is characterized in that fine particles are dispersed in the amorphous core material.
An optical transmission body according to claim 9 is characterized in that the particle diameter of the fine particles is 50 μm or less.
According to a tenth aspect of the present invention, there is provided an illuminating device comprising the above-described optical transmission body and a light source disposed at at least one end of the optical transmission body.

  According to the present invention, since it is soft and excellent in flexibility, it can be easily arranged in an arbitrary shape even when it has a large diameter, and it can be placed in a high temperature and high humidity condition or in warm water for a long time. It is possible to obtain an optical transmission body capable of stably maintaining excellent emission characteristics for a long period of time, and an illumination device using the optical transmission body, with almost no decrease in the amount of emitted light under conditions exposed to direct sunlight or wind and rain. it can.

  The optical transmission body in the present invention is composed of a tubular clad material and an amorphous core material housed in the tubular clad material and having a higher refractive index than the inner surface of the tubular clad material. With such an optical transmission body, total reflection of light is likely to occur at the interface between the cladding material and the core material, and since the core material is amorphous, the transparency can be further improved. Loss can be reduced.

  The clad material is not particularly limited as long as it is flexible, such as plastic or elastomer, and can be easily molded. For example, polyethylene, polyamide, polyvinyl chloride, silicone resin, natural rubber, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), ethylene-tetrafluoroethylene-hexafluoride Propylene copolymer, tetrafluoroethylene-perfluoroalkoxyethylene (PFA), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride, vinylidene fluoride-4 fluoro Ethylene copolymer, vinylidene fluoride-propylene hexafluoride copolymer, tetrafluoroethylene propylene rubber, tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV), vinylidene fluoride-4 Fluorinated ethylene-propylene hexafluoride-perfluoro Chill vinyl ether copolymer, poly perfluoro butenyl vinyl ether, TFE-perfluoro dimethyl dioxolane copolymer, fluorinated alkyl methacrylate copolymer, and a fluorine-based polymer such as a fluorine-based thermoplastic elastomer. These can be used alone or in a blend of two or more. Further, for example, as shown in FIG. 14, the inner surface of a tube-shaped molded product 2 a made of transparent plastic or elastomer is coated with a coating agent 2 b having a refractive index lower than that of the core material 3 and used as the cladding material 2. You can also.

  The clad material may have an irregular shape in cross section. The irregular shape may be any shape that can be easily and reliably fixed when placed on a flat surface or the like. For example, a shape in which the contact area between the disposed portion and the optical transmission body increases, a shape that can be fixed by hooking the optical transmission body on the disposed portion, and the like, specifically, a triangle, a quadrangle, Examples of the shape include pentagons and hexagons, and the shapes shown in FIGS. 6 to 9 (in the drawings, 1 is an optical transmission body, 2 is a cladding material, and 3 is a core material).

  As a constituent material of the core material, a polymer of a polymer polyol and a hydroxy group-reactive polyfunctional compound is used as one of the constituent components from the viewpoints of flexibility and aging characteristics under high temperature and high humidity. Examples of the polymer polyol include polyoxyalkylene polyols such as polyoxypropylene polyol, polyethylene glycol and polytetramethylene ether glycol, modified polyoxyalkylene polyols such as urethane-modified polyether polyol and silicone-modified polyether polyol, and polyether ester copolymers. Examples include polyols, polycarbonate polyols, condensation polyester polyols such as adipate polyester polyols, polymerization polyester polyols such as lactone polyester polyols, and copolymers or mixtures thereof. Among these, polyoxypropylene polyol is preferable because it exhibits particularly excellent emission characteristics in high temperature and high humidity conditions and in warm water. Lactone-based polyester polyols are preferred because they are excellent in long-term heat resistance and weather resistance, and exhibit excellent emission characteristics even under conditions exposed to high temperatures. Among the lactone polyester polyols, caprolactone polyester polyol is particularly preferable.

  Examples of the hydroxy group-reactive polyfunctional compound include compounds having an N-carbonyl lactam group, halides, compounds having an isocyanate group, and compounds having a functional group derived from an isocyanate group. Examples of the compound having an isocyanate group include an aliphatic polyisocyanate, an alicyclic polyisocyanate, and an aromatic polyisocyanate. Examples of the compound having a functional group derived from an isocyanate group include a blocked isocyanate obtained by blocking an isocyanate with a known method such as lactam, and a compound having an isocyanurate obtained by multiplying an isocyanate group by a known method. These can be used alone or in a blend of two or more. Among these, a compound having an isocyanate group or a compound having a functional group derived from an isocyanate group is preferable because it exhibits excellent side emission characteristics under high temperature and high humidity conditions and in warm water. Of the compounds having an isocyanate group, alicyclic polyisocyanates are more preferred. Of the compounds having a functional group derived from an isocyanate group, those having an isocyanurate bond are more preferred.

By dispersing fine particles in the core material, a light scattering function may be imparted, and a side emission type optical transmission body that emits incident light from the circumferential direction (side surface) may be used.
As fine particles, first, as inorganic material, glass fine particles such as quartz glass and multicomponent glass, metal oxide particles such as aluminum oxide, titanium oxide and magnesium oxide, sulfate particles such as barium sulfate, carbonates such as calcium carbonate And particles. Next, as organic materials, polymethyl methacrylate (PMMA) particles, polystyrene particles, polycarbonate particles, polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene -Perfluoroalkoxyethylene (PFA), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene-ethylene copolymer (ETFE), polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene Ethylene propylene rubber, ethylene tetrafluoride-hexafluoropropylene-vinylidene fluoride copolymer (THV), polyperfluorobutenyl vinyl ether, TFE-perfluorodimethyldioxolane copolymer, fluorinated alkyl methacrylate copolymer Including particles of a fluorine-based polymer such as a fluorine-based thermoplastic elastomers. These take into account the constituent material of the core material to be used, non-fluidization processing conditions, the length of the optical transmission body, the amount of light emitted from the side surface, the usage conditions, or the true specific gravity, shape, particle size, concentration, refractive index, etc. And may be selected as appropriate.

  The particle size of the fine particles is preferably 50 μm or less because the fine particles can maintain a uniform dispersed state during non-fluidization treatment, and a uniform side emission characteristic can be obtained. However, the particle diameter is not limited to the above numerical values. For example, the constituent material of the core material to be used and the non-fluidization treatment conditions, the length of the optical transmission body, the amount of light emitted from the side surface, the use conditions, or the fine particles What is necessary is just to select suitably in consideration of true specific gravity, a shape, a density | concentration, a refractive index, etc. In short, it is only necessary to examine and select the conditions under which the fine particles can maintain a uniform dispersed state during the non-fluidization treatment.

  The cladding material and / or the core material contains a weather resistance additive. Specifically, the weathering additive is added to the core material, the weathering additive is added to the cladding material, the weathering additive is applied to the inner surface of the cladding material, and the weather resistance is applied to the outer surface of the cladding material. It is conceivable to apply a sex additive. Examples of weathering additives include salicylic acid derivatives, benzophenone-based UV absorbers, benzotriazole-based UV absorbers, hindered amine-based light stabilizers, semicarbazone-based light stabilizers, and combinations thereof, antioxidants, and heat stabilizers. And combined use. Among these, a semicarbazone light stabilizer is preferable because it exhibits excellent ultraviolet resistance. Examples of the semicarbazone light stabilizer include (1,6-hexamethylenebis (N, N dimethyl semicarbazide)), (1,1,1 ′, 1′-tetramethyl-4,4 ′ (methylenedi-P-phenylene). (Bullet Retrie (hexamethylene-N, N-dimethylsemicarbaside), etc. Among these weathering additives, if it is a non-aromatic compound, the cladding material or the core material It is preferable because coloring can be prevented.

  A light-transmitting resin coating may be formed on the outer periphery of the cladding material as necessary. The constituent material of the light-transmitting resin coating is not particularly limited as long as it is a transparent and light-transmitting material, but preferably has good extrusion moldability and excellent transparency and mechanical properties. Examples thereof include vinyl chloride, ABS, polystyrene, polyallomer, cellulose acetate, cellulose butyrate, propionate, ethyl cellulose, polycarbonate, polypropylene, EVA, soft vinyl chloride, polymethyl methacrylate, and polyurethane. Further, the light-transmitting resin coating may contain the above-mentioned weather resistance additive. Specifically, a weathering additive is added to the light-transmitting resin coating, a weathering additive is applied to the inner surface of the light-transmitting resin coating, and a weather-resistant additive is added to the light-transmitting resin coating. The thing of apply | coating etc. can be considered.

  Among the materials constituting the above-described light-transmitting resin coating, those having a light transmittance of 80% or more in the visible light region at a thickness of 0.25 mm are preferable. By doing this, light scattering and absorption inside the cladding material can be suppressed, so that transmission loss can be reduced and clear light of the color intended by the design can be obtained when emitting colored light. It becomes possible to release with color. The light transmittance in the visible light region is measured according to JIS K 7105 (1981). Moreover, as a material which comprises the above-mentioned light transmissive resin coating | cover, the thing whose heat-resistant temperature is 100 degreeC or more is preferable. By doing so, the heat resistance as the optical transmission body can be improved, and the light-transmitting resin coating is deteriorated by the heat that makes the core material non-fluidized when manufacturing the optical transmission body. Can be prevented.

  The light-transmitting resin coating may have an irregular shape in cross section as long as it can be easily and reliably fixed when placed on a flat surface or the like. For example, a shape in which the contact area between the disposed portion and the optical transmission body increases, a shape that can be fixed by hooking the optical transmission body on the disposed portion, and the like, specifically, a triangle, a quadrangle, Examples include pentagonal and hexagonal shapes (in the figure, 1 is an optical transmission body, 2 is a cladding material, 3 is a core material, 4 is a light-transmitting resin coating) Show.) The light-transmitting resin coating 4 may be formed over the entire length of the optical transmission body, or may be formed only on a part thereof.

  The optical transmission body in the present invention is manufactured by the following method using the above-described constituent materials, for example. First, the clad material is formed into an irregularly shaped tube by extrusion or the like. Next, the clad material is filled with at least a polymer polyol in a fluid state and a hydroxy group-reactive polyfunctional compound. Here, “at least” is sufficient if it contains a polymer of a polymer polyol and a hydroxy group-reactive polyfunctional compound as a constituent component, and it is a matter of course that other components such as a weather resistance additive are included. However, it is assumed. In addition, when it is set as a side emission type optical transmission body, it mixes and fills with a fine particle according to this time. Further, the polymer polyol and the hydroxy group polyfunctional compound are reacted by, for example, heating to perform a non-fluidization treatment. Here, before filling the inside of the cladding material with the mixture of the polymer polyol and the hydroxy group-reactive polyfunctional compound (and fine particles) in a fluid state, the polymer polyol and the hydroxy group polyfunctional compound are subjected to pretreatment such as heating. It is conceivable to increase the viscosity. By doing so, the time for non-fluidization treatment can be shortened, and in the case of a side emission type optical transmission body, the dispersion state of the fine particles can be made more uniform.

  Examples of the method for filling the clad material with a mixture of the polymer polyol in a fluid state, the hydroxy group-reactive polyfunctional compound, and the fine particles in the clad material include a method using a vacuum pump and a tube pump, and a method of pressure filling. It is done. As another method, for example, when a clad material is formed into a tube shape by an extrusion molding method, a method of simultaneously filling a mixture of a polymer polyol, a hydroxy group polyfunctional compound, and fine particles in a fluid state is also conceivable. By doing so, it is possible to continuously manufacture a long optical transmission body.

  When forming a light-transmitting resin coating, the cladding material is extruded and coated with a light-transmitting resin on the outer circumference before filling the clad material with a polymer polyol in a fluid state and a hydroxy group-reactive polyfunctional compound. A method in which a clad material is first filled with a polymer polyol in a fluid state and a hydroxy group-reactive polyfunctional compound, non-fluidized, and then a light-transmitting resin coating is formed by extrusion coating; For example, a tube-shaped light-transmitting resin coating may be placed on the outer periphery of the clad material. Among these methods, if the cladding material is filled with a polymer polyol in a fluid state and a hydroxy group-reactive polyfunctional compound before filling the outer periphery of the cladding material with a light-transmitting resin, manufacturing is possible. It is easy and the clad material and the light-transmitting resin coating are surely adhered to each other, and the core material is not exposed to heat during extrusion coating of the light-transmitting resin, so that the optical transmission body is obtained. It is preferable because sometimes the characteristics are not deteriorated.

  In the present invention, it is also conceivable that a light source is disposed at at least one end of the above-described optical transmission body to provide an illumination device 10 as shown in FIG. As the light source 5, a conventionally known light emitting element, for example, an LED (light emitting diode) or an LD (laser diode) can be used. Further, the light emission color and the number of the light sources 5 are not particularly limited. For example, the light emission color is appropriately selected from LEDs such as red, blue, green, yellow, orange, white, or a plurality of LEDs. By combining these, various color developments can be obtained and the amount of light can be increased.

  When a side-emission type optical transmission body that emits incident light from the circumferential direction (side surface) is used as the optical transmission body 1, a light source is disposed not only at one end of the optical transmission body 1 but also at both ends. Is also possible. By doing so, it becomes possible to obtain light emission with higher luminance, and by using the light sources 5 of different emission colors at the respective ends, light emission is performed while gradually changing the color in the length direction of the illumination device 10. It can also be used for various decorative expressions.

  Further, when the optical transmission body is held in a bent state, as illustrated in FIGS. 3 to 5, fixing means 6 that can fix and hold the optical transmission body in a bent state may be used. At this time, as shown in FIG. 3, if at least one end surface of the optical transmission body 1 is held on the same plane as at least a part of the plane of the fixing means 6, Since deformation and positional deviation do not occur, the following effects are obtained, which is preferable. First, when the end face of the light transmission body 1 on the light source 5 side is fixed, the distance between the light source 5 and the end face of the light transmission body 1 can be obtained with good reproducibility, so that the amount of light incident on the light transmission body 1 is uniform. It will be something. For this reason, when mass production is performed, variations in the amount of emitted light are reduced, and quality can be stabilized. Further, when the other end face of the light transmission body 1 is fixed to the light source 5 side, it is possible to stabilize the emission direction when emitting light from the end face, so that the amount of light to the irradiated object becomes uniform, Beautiful decoration is possible.

  Below, with reference to FIG. 1, the Example regarding the edge emission type optical transmission body of this invention is described with a comparative example.

Example 1
As the material constituting the core material 3, 10 g of polyoxypropylene triol and 10 g of polyoxypropylene diol are used as the polymer polyol, 20 g of hexamethylene diisocyanate is used as the hydroxy group-reactive polyfunctional compound, and further as a weather resistance additive. 1 g of (1,6-hexamethylenebis (N, N dimethyl semicarbazide)) (HN-130, manufactured by Nippon Hydrazine Kogyo Co., Ltd.) was added. Further, as a tube constituting the clad material 2, a tube made of FEP and having an outer diameter of 3.6 mm is used. The tube was filled with the material constituting the core material 3 and heated at 100 ° C. to give the core material 3 a non-fluidization treatment, and both ends were cut to obtain the optical transmission body 1.

Example 2
As a material constituting the core material 3, 12 g of polyoxypropylene triol and 12 g of polyoxypropylene diol are used as the polymer polyol, and 13 g of Cosmonate NBDI (manufactured by Mitsui Takeda Chemical Co., Ltd.) is used as the hydroxy group-reactive polyfunctional compound. Further, an optical transmitter was prepared in the same manner as in Example 1 except that 1 g of (1,6-hexamethylenebis (N, Ndimethylsemicarbazide)) (HN-130, manufactured by Nippon Hydrazine Kogyo Co., Ltd.) was added as a weather resistance additive. 1 was obtained.

Example 3
As a material constituting the core material 3, 10 g of polyoxypropylene triol and 10 g of polyoxypropylene diol are used as a polymer polyol, and 20 g of coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) as a hydroxy group-reactive polyfunctional compound having an isocyanurate bond. And 1 g of (1,6-hexamethylenebis (N, Ndimethylsemicarbazide)) (HN-130, manufactured by Nippon Hydrazine Kogyo Co., Ltd.) was added as a weather resistance additive in the same manner as in Example 1. Thus, an optical transmission body 1 was obtained.

Comparative Example 1
An optical transmission body 1 was obtained in the same manner as in Example 1 except that the weather resistance additive was not added as a material constituting the core material 3.

Comparative Example 2
An optical transmission body 1 was obtained in the same manner as in Example 2 except that the weather resistance additive was not added as a material constituting the core material 3.

Comparative Example 3
An optical transmission body 1 was obtained in the same manner as in Example 3 except that the weather resistance additive was not added as a material constituting the core material 3.

Comparative Example 4
An optical transmission body 1 was obtained in the same manner as in Example 1 except that a PMMA plastic material was used as the core material 3.

Comparative Example 5
An optical transmission body 1 was obtained in the same manner as in Example 1 except that a commercially available two-component mixed polyorganosiloxane was used as the core material 3.

  Here, in order to evaluate the characteristics of the edge-emitting optical transmission body according to this example, the following tests were performed.

Observation of end face condition:
The cut surfaces at both ends of each sample were visually observed. The results are shown in Table 1.
Flexible:
One end of an optical transmission body 1 having a length of 100 mm from which a weight of 50 g was suspended was fixed in a horizontal state, and a distance of bending with respect to a horizontal plane was measured. The results are shown in Table 1.
Optical transmission characteristics:
(A) Initial emission characteristics Each sample of 1000 mm was arranged in a linear state, and the light quantity retention rate was measured. The light quantity retention rate was calculated by measuring the light quantity emitted from the white LED and the quantity of light emitted from the other end when the white LED was incident from one end of the optical transmission body 1 to be measured using an illuminometer. . [Light quantity retention rate (%) = light quantity emitted from light transmission body / LED light quantity × 100]
The results are shown in Table 1.
(B) Transmission loss value The transmission loss value of each sample was measured by a 3m-1m cutback method using a white LED as a light source. The results are shown in Table 1.
(C) Heat resistance (light intensity)
Each sample was left in a thermostatic bath at 200 ° C. for 1 minute, then taken out, left at room temperature for 30 minutes, the change in the light quantity retention rate was measured in this state, and the calculation was performed using the following formula.
[Light intensity change rate (%) = light intensity after test / light intensity before test × 100]
The results are shown in Table 1.
(D) Bending characteristics The light quantity retention rate is measured in a state where each sample is bent into a semicircle of 13.5 to 3.5 times its own diameter, and the change from the light quantity retention ratio obtained in the above initial characteristic test. The rate was calculated. The results are shown in FIG.
(E) Warm water resistance characteristics Each sample was left in 60 ° C. warm water for a predetermined time and then taken out and left at room temperature for 30 minutes. The results are shown in FIG.
(F) Long-term heat resistance (yellowness)
Each sample was left in a constant temperature bath at 120 ° C. for 100 hours and then taken out, left at room temperature for 30 minutes, the change in the light quantity retention rate was measured in this state, and the yellowness was calculated using the following formula.
[Yellowness = 100 × (1.28X−1.06Z) / Y]
For the values of X, Y, and Z, tristimulus values obtained from luminance meter measurement were used. The results are shown in Table 2.
(G) Weather resistance (yellowness)
Each sample was exposed to the following conditions with a xenon weather meter to evaluate the yellowness after the test.
(1) 63 ° C., 50% RH × 156 minutes (2) 20 ° C. pure water spray, 95% RH × 24 minutes During this period, 300-400 nm, 180 W / m ² continuous UV irradiation (1), (2) as one cycle The results for 125 cycles are shown in Table 2.

  From these test results, the following was found. First, although it is an end surface state, the optical transmission body 1 by a present Example had a smooth cut surface, and the grinding | polishing process of the end surface, etc. were unnecessary. On the other hand, the optical transmission body of Comparative Example 4 had to be polished for about 20 seconds because the cut surface had irregularities.

  Next, although it was flexible, the thing by a present Example was remarkably excellent in flexibility compared with the comparative example 4. FIG.

  Next, regarding the initial emission characteristics, all of the samples according to the present example showed excellent light quantity retention. Example 2 using an alicyclic polyisocyanate as the hydroxy group-reactive polyfunctional compound constituting the core material 3 and Example 3 using an isocyanurate bond as the hydroxy group-reactive polyfunctional compound are as follows: In particular, the light quantity retention rate was excellent.

  Next, as for transmission loss values, the values according to the present example are all about 1 decibel per meter or less, indicating sufficient optical transmission performance. Example 2 using an alicyclic polyisocyanate as the hydroxy group-reactive polyfunctional compound constituting the core material 3 and Example 3 using an isocyanurate bond as the hydroxy group-reactive polyfunctional compound are as follows: In particular, it showed excellent transmission loss values.

  Next, regarding heat resistance, none of the samples according to this example were deformed and there was almost no decrease in the amount of light. On the other hand, Comparative Example 4 was deformed by heating at 200 ° C. and could not be measured.

  Next, regarding the bending characteristics, the sample according to the present example showed a light quantity retention rate superior to that of Comparative Example 4. Further, according to the present example, the core material 3 and the clad material 2 were not peeled even when the bending radius was three times the self-diameter.

  Next, with regard to hot water resistance, all of the examples according to the present example had little decrease in the amount of light in warm water, and maintained excellent optical transmission characteristics stably for a long period of time. Example 2 using an alicyclic polyisocyanate as a hydroxy group-reactive polyfunctional compound constituting the core material 3, and Example 3 using an isocyanurate bond as a hydroxy group-reactive polyfunctional compound Showed particularly excellent hot water resistance. On the other hand, Comparative Example 5 using polyorganosiloxane as the core material 3 became cloudy after 50 hours, making it impossible to measure the amount of emitted light.

  Next, regarding long-term heat resistance (yellowness), according to the present example, even when heated at 120 ° C. for 100 hours, the yellowness is suppressed to 60 to 80 and shows excellent heat resistance. It was. On the other hand, it was confirmed that those according to Comparative Examples 1 to 3 in which no weathering additive was added had a yellowness of 110 or more and yellowed.

  Next, regarding weather resistance (yellowness), according to the present example, the yellowness was suppressed to 60 to 70 even after the test with the xenon weather meter was completed, and excellent weather resistance was exhibited. . On the other hand, those according to Comparative Examples 1 to 3 in which no weathering additive was added had a yellowness of 120 or more and were confirmed to be yellowed.

  Next, with reference to FIG. 1, an embodiment of the side emission type optical transmission body of the present invention will be described together with a comparative example.

Example 4
As the material constituting the core material 3, 10 g of polyoxypropylene triol and 10 g of polyoxypropylene diol are used as the polymer polyol, 20 g of hexamethylene diisocyanate is used as the hydroxy group-reactive polyfunctional compound, and further as a weather resistance additive. 1 g of (1,6-hexamethylenebis (N, N dimethyl semicarbazide)) (HN-130, manufactured by Nippon Hydrazine Kogyo Co., Ltd.) was added. Further, as a tube constituting the clad material 2, a tube made of FEP and having an outer diameter of 3.6 mm is used. Further, 0.01 g of glass beads having an average particle diameter of 5 μm are used as the fine particles. The tube is filled with the material constituting the core material 3 and the fine particles, and heated at 100 ° C., the core material 3 is subjected to non-fluidization treatment, and both ends are cut to obtain an optical transmission body. 1 was obtained.

Example 5
As the material constituting the core material 3, 12 g of polyoxypropylene triol and 12 g of polyoxypropylene diol are used as the polymer polyol, and 13 g of Cosmonate NBDI (manufactured by Takeshi Mitsui Chemicals) is used as the hydroxy group-reactive polyfunctional compound. Further, light was added in the same manner as in Example 4 except that 1 g of (1,6-hexamethylenebis (N, Ndimethylsemicarbazide)) (HN-130, manufactured by Nippon Hydrazine Kogyo Co., Ltd.) was added as a weather resistance additive. A transmission body 1 was obtained.

Example 6
As a material constituting the core material 3, 10 g of polyoxypropylene triol and 10 g of polyoxypropylene diol are used as the polymer polyol, and Coronate HX (manufactured by Nippon Polyurethane Industry Co., Ltd.) is used as the hydroxy group-reactive polyfunctional compound having an isocyanurate bond. Example 4 except that 20 g was used and 1 g of (1,6-hexamethylenebis (N, Ndimethylsemicarbazide)) (HN-130, manufactured by Nippon Hydrazine Kogyo Co., Ltd.) was added as a weather resistance additive. Similarly, an optical transmission body 1 was obtained.

Example 7
An optical transmission body 1 was obtained in the same manner as in Example 4 except that 0.01 g of glass beads having an average particle diameter of 70 μm were used as the fine particles.

Comparative Example 6
An optical transmission body 1 was obtained in the same manner as in Example 4 except that the weather resistance additive was not added as a material constituting the core material 3.

Comparative Example 7
An optical transmission body 1 was obtained in the same manner as in Example 5 except that the weather resistance additive was not added as a material constituting the core material 3.

Comparative Example 8
An optical transmission body 1 was obtained in the same manner as in Example 6 except that the weather resistance additive was not added as a material constituting the core material 3.

Comparative Example 9
An optical transmission body 1 was obtained in the same manner as in Example 4 except that a PMMA plastic material was used as the core material 3.

Comparative Example 10
An optical transmission body 1 was obtained in the same manner as in Example 4 except that a commercially available two-component mixed polyorganosiloxane was used as the core material 3.

  Here, in order to evaluate the characteristics of the side-emission type optical transmission body according to this example, the following tests were performed.

Observation of end face condition:
The cut surfaces at both ends of the optical transmission body 1 were visually observed. The results are shown in Table 3.
Flexible:
One end of an optical transmission body 1 having a length of 200 mm, on which a weight of 200 g was suspended, was fixed in a horizontal state, and a distance of bending with respect to a horizontal plane was measured. The results are shown in Table 3.
Side emission characteristics:
(A) Initial characteristics About 400 mm of each sample was arranged in a linear state, and the amount of light emitted from the side surface was measured. The amount of light emitted from the side surface is determined by measuring the amount of light emitted from the side surface at a predetermined position with a white LED as a light source. The results are shown in FIG.
(B) Warm water resistance About 400 mm of each sample is left in 60 ° C. warm water for a predetermined time, taken out, and left at room temperature for 30 minutes. And the change rate of the emitted light quantity from the initial value of the side emitted light quantity was measured in the state arrange | positioned linearly. The rate of change in the amount of emitted light was calculated by measuring the amount of emitted light from the side surface at a position 200 mm from the white LED as the light source with an illuminometer. The results are shown in FIG.
(C) Uniformity About 400 mm of each sample was arranged in a straight line, and the side emission light quantity was measured. The amount of light emitted from the side surface is determined by calculating the amount of light emitted from the side surface at an arbitrary point (0 °) on the same circumference and a point (180 °) opposite the point at a position 200 mm from the white LED as the light source. Measured with a meter. The results are shown in Table 4.
(D) Each sample with a length of 400 mm was put into a combined cycle test machine for cold heat cycle, and after 10 cycles of cool and heat cycles at 85 ° C. and −40 ° C. (each temperature held for 2 hours), the shape change of each sample was visually observed. did. In addition, the change rate of the emitted light quantity from the initial value of the side emitted light quantity was measured. The rate of change in the amount of emitted light was calculated by measuring the amount of emitted light from the side surface at a position 200 mm from the white LED as the light source with an illuminometer. The results are shown in Table 4.
(E) Long-term heat resistance (yellowness)
Each sample was left in a constant temperature bath at 120 ° C. for 100 hours, then taken out, left at room temperature for 30 minutes, the change in the light quantity retention rate was measured in this state, and the yellowness was calculated using the following equation.
[Yellowness = 100 × (1.28X−1.06Z) / Y]
For the values of X, Y, and Z, tristimulus values obtained from luminance meter measurement were used. The results are shown in Table 4.
(F) Weather resistance (yellowness)
Each sample was exposed to the following conditions with a xenon weather meter to evaluate the yellowness after the test.
(1) 63 ° C., 50% RH × 156 minutes (2) 20 ° C. pure water spray, 95% RH × 24 minutes During this period, 300-400 nm, 180 W / m ² continuous UV irradiation (1), (2) as one cycle The results of 125 cycles are shown in Table 4.

  From these test results, the following was found. First, although it is in an end surface state, the optical transmission body 1 according to this example has a smooth cut surface, and polishing of the end surface is not necessary. On the other hand, the optical transmission body of Comparative Example 9 needed to be polished for about 20 seconds because the cut surface had irregularities.

  Next, although it was flexible, all of the examples were significantly more flexible than Comparative Example 9.

  Next, as for the initial emission characteristics, all of the examples were able to obtain a stable side emission light amount regardless of the distance from the light source, and showed excellent side emission characteristics. Example 5 using an alicyclic polyisocyanate as the hydroxy group-reactive polyfunctional compound constituting the core material 3, and Example 6 using an isocyanurate bond as the hydroxy group-reactive polyfunctional compound Showed particularly excellent side emission characteristics.

  Next, with regard to hot water resistance, none of the examples according to the present example had a substantial decrease in the amount of light emitted from the side surface in warm water, and the excellent side surface emission characteristic was stably maintained for a long time. Example 5 using an alicyclic polyisocyanate as the hydroxy group-reactive polyfunctional compound constituting the core material 3, and Example 6 using an isocyanurate bond as the hydroxy group-reactive polyfunctional compound Showed particularly excellent hot water resistance. On the other hand, Comparative Example 10 using polyorganosiloxane as the core material 3 became cloudy after 50 hours had elapsed, making it impossible to measure the side emission light quantity.

  Next, with respect to uniformity, all of the examples according to Examples 4 to 6 were able to obtain a uniform side emission light quantity on the same circumference. On the other hand, in Example 7 in which the particle size of the fine particles used exceeded the upper limit (50 μm) of the preferred range of the present invention, although there was no problem in actual use, there was some variation in the amount of light emitted from the side surface on the same circumference. It was observed.

  Next, although it was a cooling / heating cycle, none of the examples according to the present example had a change in the shape after the cooling / heating cycle, and the core material 3 and the cladding material 2 did not shift at the end faces. As for the rate of change in the amount of emitted light, the decrease in the amount of emitted light was hardly observed in the example. In addition, Example 5 using alicyclic polyisocyanate as the hydroxy group-reactive polyfunctional compound constituting core material 3, and implementation using an isocyanurate bond as the hydroxy group-reactive polyfunctional compound Example 6 showed a particularly excellent outgoing light amount change rate.

  Next, regarding long-term heat resistance (yellowness), according to the present example, even when heated at 120 ° C. for 100 hours, the yellowness is suppressed to 60 to 80 and shows excellent heat resistance. It was. On the other hand, those according to Comparative Examples 6 to 8 to which no weathering additive was added had a yellowness of 110 or more and were confirmed to be yellowed.

  Next, regarding weather resistance (yellowness), according to the present example, the yellowness was suppressed to 60 to 70 even after the test with the xenon weather meter was completed, and excellent weather resistance was exhibited. . On the other hand, those according to Comparative Examples 6 to 8 to which no weathering additive was added had a yellowness of 120 or more and were confirmed to be yellowed.

  The present invention is not limited to the above-described embodiments. For example, in the fourth to seventh embodiments of the present invention, the side-emission type optical transmission body that emits light over the entire circumference in the circumferential direction is illustrated, but light is emitted between the core material and the cladding material or on the outer periphery of the cladding material. It is also possible to provide a side-emission type optical transmission body having directivity capable of emitting only a specific part by providing a layer or member that reflects light or by applying a paint that reflects light. . It is also conceivable to mark characters on the surface of the clad material and make them shine in relief.

  Further, the optical transmission body according to the present invention can be formed into a shape as shown in FIG. 15, for example, since the clad material and / or the light-transmitting resin coating formed on the outer periphery thereof can be formed into an irregular shape. . With such a configuration, the optical transmission body can be easily fitted into a groove or the like formed on the surface of the housing or the like, and the arrangement work can be made very easy and reliable. In addition, since the optical transmission body according to the present invention is excellent in flexibility, the core material 3 and the clad material 2 are not peeled off due to bending even if they have an irregular shape as shown in FIG. It can be arranged in a pattern.

  As described above in detail, according to the present invention, since it is soft and excellent in flexibility, it can be easily arranged in an arbitrary shape even when the diameter is increased, and the condition is high temperature and high humidity. An optical transmission body that is capable of stably maintaining excellent emission characteristics for a long period of time, with little decrease in the amount of emitted light under conditions exposed to hot water and direct sunlight or wind and rain for a long period of time; and The used lighting device can be obtained.

It is a figure showing an Example, and is a partially notched perspective view which shows an optical transmission body. It is a figure showing an example of an embodiment and is a schematic sectional view showing an illuminating device. It is a figure showing an example of an embodiment and is a perspective view showing the state where an optical transmission object and a fixing means were fitted. It is a figure showing an example of an embodiment and is a schematic sectional view showing an illuminating device using a fixing means. It is a figure showing an example of an embodiment and is an exploded perspective view showing an illuminating device using a fixing means. It is a figure showing an example of an embodiment and is a sectional view showing an optical transmission object which made a clad material irregular shape. It is a figure showing an example of an embodiment and is a sectional view showing an optical transmission object which made a clad material irregular shape. It is a figure showing an example of an embodiment and is a sectional view showing an optical transmission object which made a clad material irregular shape. It is a figure showing an example of an embodiment and is a sectional view showing an optical transmission object which made a clad material irregular shape. It is a figure showing an example of an embodiment and is a sectional view showing an optical transmission object in which an irregularly shaped light transmission resin coating was formed. It is a figure showing an example of an embodiment and is a sectional view showing an optical transmission object in which an irregularly shaped light transmission resin coating was formed. It is a figure showing an example of an embodiment and is a sectional view showing an optical transmission object in which an irregularly shaped light transmission resin coating was formed. It is a figure showing an example of an embodiment and is a sectional view showing an optical transmission object in which an irregularly shaped light transmission resin coating was formed. It is a figure showing other embodiment, and is a partially notched perspective view which shows an optical transmission body. It is a figure showing other embodiment and is a perspective view of an optical transmission body. It is a figure which shows the result of the bending characteristic test in an end surface emission type optical transmission body. It is a figure which shows the result of the hot water resistance characteristic test in an end surface emission type optical transmission body. It is a figure which shows the result of the initial stage emission characteristic test in a side emission type optical transmission body. It is a figure which shows the result of the hot water resistance characteristic test in a side emission type optical transmission body.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Optical transmission body 2 Cladding material 3 Core material 4 Light transmissive resin coating 5 Light source 6 Fixing means 10 Illumination device

Claims (10)

In an optical transmission body composed of a tubular clad material and an amorphous core material housed in the tubular clad material and having a higher refractive index than the inner surface of the tubular clad material, the amorphous core material is : An optical transmission body comprising a polymer composed of a polymer polyol and a hydroxy group-reactive polyfunctional compound and a semicarbazone light stabilizer as at least constituent components. In an optical transmission body composed of a tubular clad material and an amorphous core material housed in the tubular clad material and having a higher refractive index than the inner surface of the tubular clad material, the amorphous core material is: An optical transmission body characterized by having a polymer which is made non-fluidized only by polymerization of a polymer polyol and a hydroxy group-reactive polyfunctional compound and a semicarbazone light stabilizer as at least components. In the optical transmission body according to claim 1 or 2,
The above-mentioned semicarbazone light stabilizer is a non-aromatic compound. The optical transmission body according to claim 1 ,
The hydroxy group-reactive polyfunctional compound is composed of a compound having an isocyanate group. The optical transmission body according to claim 1 ,
The hydroxy group-reactive polyfunctional compound is composed of a compound having a functional group derived from an isocyanate group. The optical transmission body according to claim 5, wherein
What has the functional group induced | guided | derived from the said isocyanate group contains an isocyanurate bond, The optical transmission body characterized by the above-mentioned. In the optical transmission body in any one of Claims 1-6 ,
An optical transmission body characterized in that the amorphous core material having at least a polymer comprising the polymer polyol and the hydroxy group-reactive polyfunctional compound as a constituent component contains at least a part of a gel. . In the optical transmission body according to any one of claims 1-7,
An optical transmission body, wherein fine particles are dispersed in the amorphous core material. The optical transmission body according to claim 8 , wherein
An optical transmission body, wherein the fine particles have a particle size of 50 μm or less. Lighting apparatus for optical transmission of claim 1 to 9, wherein, characterized in that a light source disposed on at least one end of the optical transmission body.

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